Functional fluid



United States Patent 3,360,467 FUNCTIONAL FLUID Kenneth L. McHugh,Kirkwood, Mo., and John O. Smith and John R. Stemniski, Swampscott,Mass., assignors to Monsanto Research Corporation, St. Louis, Mo., acorporation of Delaware No Drawing. Filed Mar. 29, 1965, Ser. No.443,665

Claims. (Cl. 252-74) This application is a continuation-in-part of ourapplication Ser. No. 182,965, filed Mar. 27, 1962, and now abandoned.

This invention relates to liquid fluids of high thermal stability andmore particularly provides functional fluids, e.g., lubricants,comprising polyphenyl ethers and certain metal chelates as adjuvantstherefor.

The polyphenyl ethers are of great interest for use as lubricant basestocks because they are thermally stable to 800 F. and thus meet therequirement for high temperature stability which is demanded by new typeof aircraft. However, they do not possess outstanding lubricityproperties, particularly with respect to resistance to wear and toextreme pressures at high temperatures. Also, although the fact thatthey are oxidatively stable to about 500 F. makes them superior to otherpresently available lubricants insofar as oxidative stability isconcerned, further improvement in this area is desirable. The matter ofoxidative stability is also important when the polyphenyl ethers areemployed as other functional fluids, e.g., as heat-exchange media,hydraulic fluids, atomic reactor coolants, diffusion pump fluids, etc.However, for use as high-temperature lubricants, both lubricity andstability to oxidation could stand improvement. This is because, withrecent changes in the design of aircraft engines, there is a demand forlubricants which will perform satisfactorily under conditions far morerigorous than even contemplated in the past.

As is known in the art, petroleum lubricants generally comprise, inaddition to the petroleum base stock, additives or adjuvants whichimpart specifically desired properties to the base stock, e.g.,rust-inhibitors, anti-oxidants, extreme pressure-resisting agents,lubricity improvers, detersives, etc. The additives proposed heretoforehave been designed to accommodate the requirements of petroleum basestocks for lubrication in conventional equipment such as internalcombustion engines of the automotive type, diesel engines and the like.One feature in common with respect to these various applications wasthat the temperature of use was not excessive, i.e., it may vary fromabout 40 F. to 300 F. With the advent of extremely high speed aircraftof the jet type, it was found that neither the petroleum base stock northe conventional additives used therewith were practical, because thelubricant and the additives had to be effective at temperatures whichwere above the decomposition points of the known additives, e.g., attemperatures which were generally within the range of 400 F. to 700 F.It was also found that when conventional additives were employed withlubricants and other functional fluids having higher thermal stabilitythan that possessed by petroleum base stocks, the additives did notperform in a predictable manner, i.e., a material possessing an extremepressure-resisting effect or an antioxidant effect with the petroleumhydrocarbon 3,360,467 Patented Dec. 26, 1967 lubricants generally didnot possess such effects when used with the polyphenyl ether fluids.

Since the polyphenyl ether fluids are not exceptional in their abilityto lubricate metals, lubricity additives are generally required toprevent excessive wear of moving metal parts. Such an additive must notonly be stable at the high temperatures to which the polyphenyl etherlubricant is exposed during use, but it must also be noncorrosive to themetal under such conditions. Also, it should not catalyze decompositionand/or oxidation of the polyphenyl ethers at the high temperatures. Ifan extraneous antioxidant or corrosion-inhibiting agent is preent, theanti-wear additive must be non-reactive toward it. Hopefully, theanti-wear additive should also be an antioxidant for the polyphenylethers. Inhibiting oxidation of the polyphenyl ethers at the hightemperatures is necessary in order to avoid an increase in viscosity ofthe fluid to the point where it can clog up the mechanism. Since theethers with which the present invention is concerned are entirelyaromatic, oxidation proceeds in a manner which differs essentially fromthat of compounds having aliphatic carbon. The mechanism whereby thepolyphenyl ethers are oxidized at high temperatures is unique comparedto the classical mechanisms depicted for the low temperatureautooxidations of, e.g., the petroleum hydrocarbons. In the case of thepolyphenyl ethers, the initiation step is an attack by molecular oxygenat the phenyl-oxygcn-phenyl carbons rather than at the OH positions asin the case of the parafiinic hydrocarbons. Thereby, there is formed aphenoxy free radical which adds to a poiyphenyl ether molecule to formhigher molecular weight, fused-ring polyphenyl ethers. Deterioration ofthe polyphenyl ether is thus demonstrated not by carbonization, but bygreatly increased viscosity owing to presence of the very high molecularweight ethers. However, in arriving at a satisfactory lubricity andantioxidant additive for the polyphenyl ethers, the possibility ofsludging cannot be over-looked, since use of some additives at the highoperating temperatures will result in sludging, even though antioxidanteffect is evidenced by lack of viscosity increase in the polyphenylether fluid. On the other hand, additives whoseuse does not bring aboutthe formation of sludge may be found to be ineffective insofar aspreventing viscosity increase is concerned.

Accordingly, an object of the present invention is the provision ofimproved polyphenyl ether fluid compositions. Another object of theinvention is the provision of polyphenyl ether lubricants havingimproving resistance to wear. Still another object is the provision ofpolyphenyl ether compositions which possess an improved resistance tooxidation. A most important object is provision of polyphenyl etherfluids which are substantially nonsludging.

These and other objects hereinafter disclosed are provided by theinvention wherein there is employed as additives for the polyphenylether liquid fluids a chelate of a heavy metal of Groups I-IV andVI-VIII of the Periodic Arrangement ofElements and a carbonyl compoundof the formula in which R and R are selected from the class consistingof alkyl radicals from 1 to 6 carbon atoms and aryl, alkaryl and aralkylradicals of from 6 to 10 carbon atoms, and Z is selected from the classconsisting of hydrogen, R, R, and carboalkoxy radicals of from 2 to 6carbon atoms.

It will be evident from the above formula that the invention encompassesas additives having one or more effects on thepolyphenyl ethers certainmetal chelates of aliphatic fl-diketones. The metal constituent of thechelate may be, for example, copper, silver or gold of Group I of thePeriodic Arrangement of Elements, zinc, cadmium and mercury of Group II,aluminum, gallium, indium and thallium of Group III, titanium,germanium, zirconium, tine and lead of Group IV, manganese and rheniumof Group VII, and iron, cobalt, nickel, ruthenium, palladium, iridiumand platinum of Group VIII.

The carbonyl compound may be an aliphatic or aliphatic-aromatichydrocarbon B-diketone, e.g., acetylacetone,1,5-diphenyl-2,4-pentanedione, tridecane-4,6-dione,1-p-tolyl-3,5-octanedione, 3-benzyl-2,4-pentanedione or1,7-di-B-naphthyl-3,S-heptanedione. The carbonyl compound may or may notcarry a carboalkoxy group at the carbon atom which is between the twocarbonyl groups, e.g., it may be 3-carbomethoxy-2,4-pentanedione, 4-carbopentyloxy-l-phenyl-3,5-hexanedione, or3-carbobutoxy-1,6-di-u-naphthyl-2,4-pentanedione.

Owing to their easy availability, a very useful class of chelates isthat obtained from acetylacetone. For convenience, these will behereinafter referred to as metal acetylacetonates. They are readilyavailable in known manner by reaction of acetylacetone with a salt ofthe appropriate metal, e.g., the acetate, chloride or sulfate. Examplesof presently useful metal acetylacetonates include the copper, zinc,cadmium, aluminum, zirconium, ferrous, ferric, cobalt, manganous, nickeland indium acetylacetonates.

Other metal chelates of paraflinic B-diketones which can be used. asantioxidants for the polyphenyl ethers include:

Manganous. chelate of 2,4-hexauedione,

Cadmium chelate of 3-methyl-2,4-pentanedione,

Aluminum chelate of 3,5-heptanedione,

Zirconium chelate of 3,5-octanedione,

Titanium chelate of 2,4-decanedione,

Tin chelate of 7, 9-pentadecanedione,

Ferrous chelate of 3-butyl-2,4-pentanedione,

Iridium chelate of 3-hexyl-4,6,-nonanedione,

Germanium chelate of 3,5-heptanedione.

The polyphenyl ethers to which this invention pertains can berepresented by the structure where. Iris a whole number from 2 to Thepreferred polyphenyl ethers are those having all their other linkagesinthe meta position since the all-meta linked ethers are the best suitedfor many applications because of'their wide range and high degree ofthermal stability. However, mixtures of the polyphenyl ethers, i.e.,either isomeric mixtures or mixtures of homologous ethers, can also beused to obtain certain properties, e.g., lower solidification points.Examples of the polyphenyl ethers contemplated are thebis(phenoxyp-henyl) ethers, e.g., bis(m-phenoxyphenyl) ether, thebis(phenoxyphenoxy)- benzenes, e.g., m-bis(m-phenoxyp henoxy)benzene,mbis(p phenoxyphenoxy)benzene, o bis(o phenoxyphenoxy)benzene, thebis(phenoxy phenoxyphenyl) ethers, e.g., bis[m-(m-phenoxyphenoxy)phenyl]ether,

bis [p- (p-phenoxyphenoxy) phenyl] ether, m- L (m-phenoxyphenoxy)phenyl]o-[(o-phenoxyphenoxy)phenyl] ether and the bis(phenoxyphenoxyphenoxy)-benzenes, e.g., m-bis [m- (m-phenoxyphenoxy) phenoxy benzene, p-bis[1(m-phenoxyphenoxy)phenoxy1benzene, orm-bis[m-(pphenoxyphenyl)phenoxyJbenzene. It is also contemplated thatmixtures of the polyphenyl ethers can be used. For example, mixtures ofpolyphenyl ethers in which the non-terminal phenylene rings (i.e., thoserings enclosed in the brackets in the above structural representation ofthe polyphenyl ethers contemplated) are linked through oxygen atoms inthe meta and para positions, have been found to be particularly suitableas lubricants because such mixtures possess low solidification pointsand thus provide compositions having wider liquid ranges. Of themixtures having only meta and para linkages, a preferred polyphenylether mixture of this invention is the mixture of S-ring polyphenylethers where the non-terminal phenylene rings are linked through oxygenatoms in the meta and para position and composed, by weight, of aboutim-bis(m-phenoxyphenoxy)benzene, 30%m-[(mphenoxyphenoxy)-(p-phenoxyphenoxy)]benzene and 5%m-bis(p-phenoxyphenoxy)benzene. Such a mixture solidifies at about -l0F., whereas the three components solidify individually at temperaturesabove normal room temperature.

The aforesaid polyphenyl ethers can be obtained by the Ullmann ethersynthesis which broadly relates to ether forming reactions, e.g., alkalimetal phenoxides such as sodium and potassium phenoxides are reactedwith aromatic halides such as bromiobenzene in the presence of a coppercatalyst such as metallic copper, copper hydroxides, or copper salts.

The metal chelates are combined with the fluid polyphenyl ethers to theextent of 0.01% to 1.0% by weight, depending upon the nature of theindividual chelate and of the ether fluid. Within these limits, theconcentration of chelate at which the desired effects are obtained willvary, depending upon the nature of the chelate and of the polyphenylether. It may be readily determined by use of conventional testingprocedures known to those skilled in the art. The present chelatespossess anti-wear and anti-oxidant effects on the polyphenyl ethers,generally.

The invention is further illustrated by, but not limited to, thefollowing examples:

EXAMPLE 1 Manganous and lead acetylacetonates were compared with somecommonly employed lubricant additives for anti-wear effect whenincorporated into a mixture of polyphenyl ethers consisting byweight of:

Testing was conducted by means of the Shell 4-Ball Wear Machine. Itconsists of an equilateral tetrahedron formed by 4" stainless steelballs with the three lower balls immovably clamped in a ball holder. Inthe present tests, the upper ball was'rotated about the vertical axis incontact with the 3 lower stationary balls under a 40 kg. load for onehour at400 F. The contacting surfaces were immersed in the test fluidand the circular scars worn in the surface of the three stationary ballswere measured by means of a low power microscope. A modified cup andheater assembly was used to evaluate lubricants at the 400 F.temperature; see The Study of Lubrication Using the Four-Ball TypeMachine, R. G. Larsen, Lublic-ation Engineering, 1, pages 35-43, 59,August 1945.

Employing the above procedure, the results shown in ,5 Table I wereobtained with the additives shown therein at the indicatedconcentrations:

TABLE I Concn., Scar Additive weight diameter,

percent mm.

None 3.30 Manganous acetylacetonat 0.5 1. 19 Lead acetylacetonate..." 0.5 1. 18 Bis (triphenylphosphine)nickel dibromid 0.5 3. 45Diphenylmercury 1. 3. 32 Tropylidcne molybdenum tricarbonyl 0.5 3. 31Boron trifiuoride/N i dimethylglyoxime complex. 1.0 3. 38Bis(triphenylphosphine)nickel dithioeyanate.. 0. 3. 392,4,6triphenylphenol 1. 0 3. 36 N-nitroso-N-phenylbenzylamine. 1. 0 3.04 2,2dipyridylamine 1. 0 3. 53

EXAMPLE 2 The mixture of polyphenyl ethers described in Example 1 wereincorporated with ferric or with manganous acetylacetonate and thensubmitted to the F'alex test for the purpose of determiningextreme-pressure resisting properties. This test is described in thearticles by V. A. Ryan in Lubrication Engineering, September 1946, andby S. Kyropoulos in Refiner Natural Gasoline Mfr., 18, 320-24 (1939).Briefly, the test was conducted as follows:

There was employed a Faville-LeVally Falex lubricant testing machinewith heating element, 4,500 lb. pressure gage indicating bearing loads,calibrated, circular, toothed loader capable of providing wearestimates, and torque indicating gage. The machine is essentially adevice in which a pin 'is rotated between two V-shaped bearing blockswhich are immersed in an oil cup containing '55 ml. of the lubricantwhich is to be tested. The bearing blocks are inserted in self-aligningrecesses in the short lever arms, or jaws, ofthe loading-applyingmechanism. Pressure is applied through the loading mechanism which fitsloosely over the bifurcated ends of the long level arms. The ratchetwheel is turned up by hand until the loading mechanism takes hold, whichis indicated by registration of applied load on its attached gage.Additional load is applied by engaging the load-applying arm with theratchet wheel. The eccentric motion of the loada'pplyingarm increasesthe application of load, one tooth at a time. The entire mechanism isfree to swing about its axis, this tendency to turn being resisted bythe syphon operated gage which registers torque in pound-inches. In thepresent tests, the machine was operated at 290 rpm.

' Employing the above-described procedure, the Falex reading for saidmixture of polyphenyl ethers containing a 1.0% by weight concentrationof ferric acetylacetonate was 1750 and that for said mixture ofpolyphenyl ethers containingjan 0.5% concentration of manganonsacetylacetonate was 2250. That for the same mixture of poly- 'phenylethers in absence of any additive was 500.

EXAMPLE 3 A number of 'metal acetylacetonates were compared with somecommonly employed lubricant additives for inhibition of viscosityincrease at high temperature in the presence of oxygen. The base stockwas the mixture of polyphenyl ethers described in Example 1. Testing wasconducted as follows:

Samples were prepared consisting of 20 ml. of said mixture of ethers andthe concentration of additive shown below. The sample was heated to 100F., and the viscosity of the sample was determined at this temperature.The temperature was then increased to 600 F., and while holding thesample at this temperature, air was bubbled through it at a rate of 1liter per hour, for either 24 or 48 hours as shown below. The sample wasthen allowed to cool, the viscosity was re-determined at 100 F., and thepercent increase in viscosity was calculated. The results shown in TableII were obtained.

TABLE II Concn. Time, Viscosity Additive percent hours Increase,

weight percent 00 acetylacetonate".-. 0.5 24 10.9 Mn acetylacetonate 0.5 24 10. 1 Ni acetylacetonate.-. 0. 5 24 12. 9 Fe acetylacetonate. 0.524 16. 8 Ti acetylacetonate-.. 0.5 24 19. 9 Al acetylacetonate... 1.0 2420. 7 In acetylacetonate 0.5 48 20. 2 Cu chelato of2-pheny1-2-n1ercaptoethylphenyl ketone 1. 0 48 45. 9 Tin titaniummalonate 0.5 48 40. 2 Bis(N,N-dimethylamino)titanium dichloride 0. 5 4890. 6 Diphenyltin bis(didecyldithiophosphate) 1. 0 48 123. 0 Reactionproduct of hydroquinone and dibutyltin oxide 0.5 48 56. 2 Tropylidenemolybdenum tricarbonyL. 0.5 24 173.0 Bis (p-phenoxyphenyl)mercury. 1. 024 48. 2 Ni bis (N -phenyl-5-nitrosalieylimine) and trichloroacetic acid(2:1) 3. 0 24 64 Diphenylamine 1. 0 24 73. 3 2,4,6-triphenylphenol 1. 024 59. 0 Phenylbiphenylamine 1. 0 48 116. 9Triphenylphosphine/triphenylboron complex 1. 0 24 67. 7Tetraphenylsilaue 1. 0 24 52. 1 Tetraphenylgermane 0. 5 24 53. 0Triphenylarsine 1. 0 24 50. 0

EXAMPLE 4 The effect of the presence of some metals on inhibition ofviscosity increase by various additives, including variousacetylacetonates, is described in this example.

Respective samples of the mixtures of ethers of Example 1 wereincorporated with the concentration of additive noted below and the samequantity in each case of pieces of copper, aluminum and steel wire. Airwas passed through the samples at the rate of 1 liter per hour for thetime shown below while maintaining the samples at 600 F., and theincrease in viscosity thereby produced was determined at F. The resultsshown in Table III were thereby obtained:

TABLE III Conan. Time, Viscosity Additive percent hours Increase,

weight percent Co acetylacetonate 0. 5 24 4. 9 Cu acetylacetonate. 0.524 10.0 Ferrous acetylacetonate. 0.5 24 15. 2 Mn acetylacetonate 0. 5 2415. 4 Aluminum acetylacetonate 1. 0 24 13. 2 Ti acetylacetonate 0. 5 2413. 0 Nickel acetylacetonate. 1. 0 24 24. 3 Ferric acetylacetonate. 1.024 24. 5 In acetylacetonate 0. 5 48 12. 1 Bis(tributylphosphine)nickelchloride. 1. 0 24 83. 0 Tripyridylmolybdenum tricarbonyl. 0.5 24 107.2Triphenylphosphinemolybdcnum pentaearbonyl 0.5 24 134.1 o-Biphenylsilicate 1. 0 24 150. 5 Ni ehelate of 2-pl1enyl-2-mercaptoethyl.

phenyl ketone I. 0 48 156. 0 Ni bis(N-p-phenoxyphenoxyphenyl-5-nitrosalicylimine) i 2. 0 24 122. 0 o-tert-Butylaniline 1. 0 24 113. 92,6 di-tert-butyl-4-methylaniline 1.0 24 204. 7 p-Tolyl sulfoxide 1. 024 111.4

EXAMPLE 5 In this example there are shown the simultaneous anticorrosiveand viscosity-increase inhibiting effects of cobalt acetylacetonate andof titanium acetylacetonate as compared to other additives. Testing wasconducted as follows:

Respective samples of the mixture of ethers described in Example 1 wereincorporated with the concentration of additive shown below in Table IVand with the same quantity in each sample of metallic copper, steel,aluminum, silver and titanium. The viscosity of each sample wasdetermined at 100 F. Air was then passed through each sample at the rateof 1 liter/hour for 24 hours While [(m-phenoxyphenoxy) (ophenoxyphenoxy')1benzene, or m-bis[m-(p-phenoxyphenoxy')phenoxy]benzene,or mixtures thereof in any proportion. Lubricant mixtures of ethers aregenerally so constituted as to give si'multaneously an optimum ofthermal stability and lubricity at TABLE IV Viscosity Additive Increase,Cu Steel Al Ag Ti Percent Co'acetylacetonate, 0.5% 4. 4 0. 32 0.32 0.120. 12 0.00 Ti acetylacetonate, 0.5% 8.8 0. 24 0. 04 O. 20 0. 04 0.95 Bis(triphenylphosphine) iron trica-rbonyl, 0.5% 13. 60 14. 20 2. 60 26. 12.70 1. 50 Thiobisphenol, 0.5% 48. 80 0. 08 0. 12 0. 08 0.08 1. 60

EXAMPLE 6 the temperatures to which they will be exposed in opera- Inthis example there are shown the simultaneous viscosity-increaseinhibiting and anti-sludging effects of cobalt acetylacetonate andferric acetylacetonate as compared to other additives. Testing wasconducted according to the procedure of specification MlL-L9236A(Federal Specification 791 Method 5308.2), which test determinesstability to oxidation in the presence of metals by determiningviscosity change and the formation of sludge; however, the tests wereconducted at 650 F. instead of at 500 F., as called for by saidspecification. In each test, the base stock was the mixture ofpolyphenyl ethers described in Example 1, and in each test the additivewas present in a.0.5% concentration. The tests were run for a period of48 hours.

The results obtained are set forth in Table V. With respect to the datain the column of the table headed Viscosity Increase, percent such datawere obtained by measuring the viscosity, at 100 F., of the polyphenylether mixture plus additive. before and after. completion of theoxidation tests and reporting the differences as a percent increasebased on the original viscosity. In the case of the column identifiedDeposit Rating, the numbers therein are ratings based on a scale from 1to 4, with 1 being essentially none and 4 heavy deposit of sludge.

The data of Table V show that while many materials serve to suppresssludging of the polyphenyl ethers under severe temperature andoxidation. conditions, the metal chelates are unique; in that theyfunction simultaneously as very good viscosity-increase inhibitors andas inhibitors of sludge deposits.

The present metal chelates contribute anti-Wear pressure-resisting,sludge-inhibiting, corrosion-resisting and antioxidant properties to thepolyphenyl ether fluids, generally. Thus, instead of the mixture of 65%by weight of m-bis(m-phenoxyphenoxy)benzene, 30% by weight of m-[m-phenoxyphenoxy) (p phenoxyphenoxy)]benzene and 5% m-bis(p-phenoxyphenoxy)benzene which was used in the above examples, thepolyphenyl other component may be any one polyphenyl ether having from 4to 7 benzene rings. For example, manganous or nickel acetylacetonate canbe a very good anti-wear additive for any one. of the. three ethers ofthe polyphenyl ether mixture of theabove examples, as well as for suchother polyphenyl ethers as p bis[p (m-phenoxyphenoxy)phenoxy1benzene ormtion; but since the polyphenyl ethers, generally, are benefited by themetal chelates with respect to increasing stability to wear' and tooxygen at high temperatures, mixtures having varying proportions of theethers are advantageously modified by the present additives.

Although the present metal chelates, generally, confer a plurality ofadjuvant effects including lubricity and antioxidant properties to thepolyphenyl ether fluids, a single metal chelate does not necessarilyimpart all of these properties to the polyphenyl ethers simultaneously.One metal chelate may be more effective than another: with respect toconferring a desired. property; and within the 0.01% to 1.0%.concentration range; a: greater, amount of a certain chelate may be.required to impart one property, e.g., antiwear. effect, than isrequired to impart. another property, e.g':, antisludging' effect.Therefore, although a plurality of the adjuvant effects. are generallydemon.- strated' by a single metal chelate, two or'more, chelates maybe' used together advantageously: one to provide a certainneifect at thelowest possibleconcentration.and another one to provide a diverseeffect, also at the lowest possible concentration. Selection of theproper metal chelate and the optimum concentration thereof for ob,-taining the desired benefit is simply a matter of routine testing by oneskilled in;the' art.

Polyphenyl other fluids. containing the present chelate additivesareparticularly useful as'high temperature lubricants because they possessgood antiwear and/ or extreme pressure. resisting property while at the.same time possessing good resistance to oxygen atvery high temperatures.However, compositionsconsisting of. the. polyphenyl ethers and thepresent chelate additives are also advantageously employed in otherfunctional fluidapplications, e.g., as hydraulic fluids and asheabexchange media. The chelate additives inhibit viscosity increase. inthe. presence of oxygen at high temperatures and also prevent sludgingand corrosion; hence, these additives. render the. poly.- phenyl etherssuitable for usev inany applicationinwhich is involved exposure to.oxygenand/or. metalattemperatures of up to, say, the decomposition pointof the polyphenyl ethers.

The metal chelates may be, used in. the polyphenyl ethers with otheradditives, e.g., pour point depressants, viscosityindex improvers, dyes,etc.

Other modes of, applying the principles. of'thisinvention may beemployed instead of these specifically set forth above, changes beingmade as regardsthe details herein disclosed, provided the elements setforth in any of. the following claims, or equivalents thereof. may beemployed.

What we claim is:

1. A liquid fluid composition consisting essentially of a polyphenylether of the formula 9 wherein n is a whole number of from 2 to 5 andfrom 0.01% to 1.0%, by weight of the ether, of a chelate of a heavymetal of Groups I-IV and VIIVIII of the periodic Arrangement of Elementsand a carbonyl compound of the formula wherein R and R are selected fromthe class consisting of alkyl radicals of from 1 to 6 carbon atoms andaryl, alkaryl and aralkyl radicals of from 6 to 10 carbon atoms and Z isselected from the class consisting of hydrogen, R, and R, andcarboalkoxy radicals of from 2 to 6 carbon atoms.

2. The composition defined in claim 1, further limited in that Z ishydrogen.

3. The composition defined in claim 1, further limited in that thecarbonyl compound is acetylacetone.

4. The composition defined in claim 1, further limited in that thechelate is cobalt acetylacetonate.

5. The composition defined in claim 1, further limited in that thechelate is manganous acetylacetonate.

6. The composition defined in claim 1, further limited in that thechelate is ferric acetylacetonate.

7. The composition defined in claim 1, further limited in that thechelate is indium acetylacetonate.

8. The composition defined in claim 1, further limited in that thechelate is lead acetylacetonate.

9. The composition defined in claim 1, further limited in that thechelate is the ferrous acetylacetonate.

10. The composition defined in claim 1, further limited in that thechelate is the nickel acetylacetonate.

References Cited UNITED STATES PATENTS 2,460,700 2/1949 Lyons 25274 X2,795,549 6/1957 Abbott et a1. 25274 X 3,006,852 10/1956 Barnum et a1.25252 FOREIGN PATENTS 851,651 10/ 1960 Great Britain.

LEON D. ROSDOL, Primary Examiner.

S. D. SCHWARTZ, R. D. LOVERING,

Assistant Examiners.

1. A LIQUID FLUID COMPOSITION CONSISTING ESSENTIALLY OF A POLYPHENYLETHER OF THE FORMULA